Poly aryl derivatives of urea and process of making same



Patented Mar. 22, 1932 UNITED sTATEs PATENT OFFICE LEOPOLD LASKA AND-OSKAR I HALDER, 0F OFFENBAGH-ON THE-MAIN, GERMANY, ASSIGNORS TO GENERALANILINE .WORKS, INC., 0]? NEW YORK, N. Y., A CORPORA- TION OF DELAWAREPOLY DERIVATIVES OF UREA AND PROCESS OF MAKING SAME No Drawing.Application filed October 23, 1929, Serial No. 401,974, and inGermany'November 2, 1928.

' Our invention relates to new urea derivatives corresponding probablyto the general formula 1 NH-R-G ONHR10H oo 1 NHR-C o-NH-R on,

wherein R and R represent aromatic residues of the benzene ornaphthalene series, which may contain further substituents, but no freesulfonic nor carboxylic acid groups and to a process of making same. Thenew compounds are obtainable by condensing diaryl-urea-dicarboxylicacids'in the presence of a phosphorus chloride with aminophenol oraminonaphthol compounds containing no free sulfonic nor carboxylic acidgroup but having at least one free orthoor para-position related to thehydroxylgroup.

The same products may be obtained by condensing aminoarylcarboxylicacids or their corresponding halogen substitution products withaminophenolsor aminonaphthols and treating the aminoaroylaminophenolsand aminoaroylaminonaphthols thus obtained with phosgene. Theseaminoaroylaminophe- 1101 and aminoaroylaminonaphthol compounds may alsobe formed by condensing nitroarylcarboxylic acids with aminophenols oraminonaphthols and reducing the condensation products.

The new compounds being object of our present invention are suflicientlysoluble in water in the form of their alkali metal salts in spite of theabsence of free sulfonic or carboxylic groups and in spite of thelargeness of their molecule. They are distinguished by a certainafiinity to cotton allowing the impregnation of cotton goods with thesolutions of-their alkali metal salts.

In order to further illustrate our invention 0 the following examplesare given, the parts tigrade degrees, but we wish it to be understoodthat .we are not limited to the particular products nor reactionconditions mentioned therein.

. Example 1 g 274 parts of para-aminobenzoic acid and 272 parts ofsodium acetate are dissolved in about 1000 parts of water and at aboutphosgene is passed into the solution until it is saturated. Thediphenylurea-dicarboxylic acid thus separating from the solution is filtered ofi, washed with hydrochloric acid and then with water and dried.It is insoluble in the usual organic solvents.

30 vparts of this diphenylurea-p.p'-dicarboxylic acid are mixed with 22parts of paminophenol and 300 parts of dimethylaniline; at about -80" 10parts of phosphorus trichloride are allowed to drop in, and finally themixture is heated at aboutvl20 for about 5 hours. Then the reaction massis poured on hydrochloric acid, the precipitate formed is filtered offand stirred with a sodi-. um carbonate solution until an alkalinereaction. The dimethylaniline is expelled by steam and the condensationproduct thus obtained may be purified by dissolving it in an alkalinesolution and precipitating it again with carbonic acid. It correspondsprobably to the formula NH CO-NH O NHOCONH Example 2 A mixture of 60parts of diphenylureap.p-dicarb0xylic acld, 48 parts of o-aminop-cresoland 400 parts of dimenthylanilineis allowedto react with 24 parts ofphosphorus trichloride as described in Example 1.v The.

reaction mass is worked up in alike manner. Thenew condensation productthus obtained corresponds to the probable formula 5 11040 o m r HIC iItmay be purified by dissolving it in an alkaline solution andprecipitating again by carbonic acid. It melts at about 215217.

When replacing o-amino-p-cresol for instance by p-amino-o-cresol,m-amino-o-cresol 'orl m-amino-p-cresol and carrying out theprocessotherwise as'described above similar products'are obtained. 1 i I'7 'Eaumiplefa 274 parts 'ofm-am'inobenzoic acid and272 7 parts ofsodium acetate are dissolved in about 1000 parts of water, and at about60 7 I ph0sgene is passed into this solution. The

hydrochloric acid, the

a o mula V diphenylurea-m.m-dicarboxylic acid thus separating from thesolution is filtered off,

'washed with hydrochloric acid and then with water-and dried. It meltsat" about parts of this diphenyl-urea-m.m'-dicarboxylic acid are'mixedwith 22 parts of maminophenol and 300 parts of dimethylaniline; and atabout-7080 1O partslof phos phorus trichloride are allowed to drop in.After having been heated at about 120 for about 5 hours the reactionmass is poured on formed is filteredofi and stirred with a sodiumcarbonate solution until an alkaline reaction. Thedimenthylanilineisexpelled by steam andthe new condensation product maybe purified as described in the foregoingexsimples. It correspondsprobably to the 6 Q f I It is insoluble inthe usual organic solvents,

' the unpurified product melts at about 255 e qmp e,v

recipitate thus 7 257 with decomposition. The reaction can be carriedout in the same manner when replacing m-aminophenol by 1.5-0r2.7-aminonaphthol or when starting from the urea derivativeof the2.3-aminonaphthojcapid.

Example 4 Into a mixtureof 30 parts of 'dephenylurew Im.m-dicarboxylicacid522parts of p-amino- 1 oo-nn-OOH" It is insoluble inthe usual organic solvent and melts in a raw state at about 255 While Ip, I Ewes Into a mixture of 167 partsofm-nitroben zoic acid,"l09 partsof 'm-aminophenol and 1500 parts of toluene at about 70-80 parts ofphosphorus trichloride' are allowed to dropin,,andthe mixture isheated'at about 110 until the evolution of hydrochlorid acid gas'ceases.The reaction mass is made alkaline by'adding sodium carbonate, thetoluene is expelled by steam and the reaction product is purified asdescribed above. It or stallizes from glacial acetic acid and melts in apure state at about 2199. v 7 129 parts of thism-nitrobenzoyl-m-aminophenol are dissolved in'about 400 parts of ammonia(density 0,91) and about 1500 partsof alcohol; the solution is heated toboiling-and then slowly 200 parts of zinc dust are added. After heatingthe mass for some hour's to boiling, the solution is filtered whilestill hot and the formed m' aminobenlzoyl-maminophenol separates oncooling in the form of a" sandy powder It crystalizes difficultly fromorganic solvents but it is soluble in glacial acetic acid.

' 228 Pa t qif i m"- in behz i mem nophenol are dissolved in', about1500 parts of glacial acetic acid and 136 parts of sodium 0 acetate.Into this solutionat about 80 phosgene is passed until the mixture issaturated.

The separating condensation product is filteredofi, washed withhydrochloric acid and water and dried It is identical with thecondensation product from diphenyluream,m'-dic arboxylic acid andni-aminophenol,

described in Example The course of the single steps of reaction tainmethyl groups, which products are in-v may be illustrated by thefollowingscheme of soluble in the usual organic solvents, but in formulaCOOH OH reduction We claim; A 1. As new compounds urea derivativescorresponding probably to the general formula:

mula

o o-NnRi o n wherein the R s represent benzene, toluene table fiber.

3. As new compounds urea derivatives corresponding probably to theformula wherein the benzene nuclei containing the hydr-oxylgroup andsignified by I may con- A oo-NHQ derivatives corresponding probably tothe general forthe form of their alkali metal salts, are'sol- MEG o oO-NHQ which product is insoluble in the usual organic solvents, theunpurified product melts at about 255-257" while decomposing, and

the alkali metal salts of which are soluble water and have afiinity tothe vegetable er. a 5L Theprocess which comprises condensing adiaryl-urea-dicarboxylic acid of the general formula:

/NHROOOH oo \NHR-OOOH wherein the Rs stand for benzene or naphthalenenuclei, in the presence of a phosphorus chloride with two molecularproportions of an amino-hydroxy compound of the general formula:

wherein R represents a benzene, toluene or naphthalene nucleus.

6. The process which comprises condensing a diaryl-urea-dicarboxylicacid of the general formula:

NHR-COOH o \NHRGOOH wherein the Rs stand for benzene or naphthalenenuclei, in the presence of phosphorus "trich1oride with two 3110 "of an'amino-hy'droxy compound of the gem,

i diphenyl-urea-m.m-dicarboxylic acid of the I formula; 1

wherein R represents a, benzene, toluene or naphthalenenucleus. r

7. The process which comprises condensingdiphenyl-urea-m.m'-dicarboxy1ic acid of the formula:

' OOOH ma- 2 v in the Presence of P o p orus chloride with I 7 twomolecular proportions of an amino-hydroxy compound of the generalformula:

r Z 1+ v, i

naphthalene nucleus. i

8. The'process which comprises condensing wherein R represents abenzene, toluene or s coon @003 in the presence of phosphorustrichloride with two molecular proportions of an amino- 7hydroxy=compoundof the general formula:

wherein R representsa benzene, toluene 01f na thalenenucleus.

n testimony whereof, we afiix oursigna, i es. p o e LEOPOLD LASKA. OSKARHALLER.

le'cular proportiohsfl

